Antisymmetric exchange and pseudo Jahn–Teller instability in spin-frustrated metal clusters

In this article, we analyze the interplay between the antisymmetric (AS) exchange interaction and Jahn–Teller (JT) vibronic coupling in spin-frustrated systems with triangular units. AS exchange in these systems creates a strong first order magnetic anisotropy related to the orbitally degenerate frustrated ground state that is analyzed for the unique structure of the cluster anion present in K 6 [ V 15 IV As 6 O 42 ( H 2 O ) ] · 8 H 2 O (V15 cluster) exhibiting layers of different magnetization. Spin-frustration inherently related to the orbital degeneracy creates a structural instability that is shown to be competitive to the AS exchange. The vibronic pseudo JT coupling arising from the modulation of the exchange interaction by the double degenerate molecular vibrations is shown to reduce AS exchange giving rise to a restoration of magnetization quenched by AS exchange. This leads to an essential reduction of the magnetic anisotropy in spin-frustrated triangular clusters so that in the limit of strong JT coupling the isotropic exchange model becomes adequate.